Porous ceramics with tri-modal pores prepared by foaming and starch consolidation

Porous silica ceramics with tri-modal pores were prepared, based on the generation of foams from silica/starch composite slurry and the subsequent stabilization of the structure by starch consolidation. The rheology of the original slurry and the foamed one were evaluated and compared. After drying, the green bodies were debindered and sintered at 1250 °C for 5 h. The resulting materials consisted of a hierarchical structure with large-sized cells, moderate-sized pores in cell wall and small-sized voids among silica grains. The compressive strength of the sintered samples varied within the range of 4–17 MPa, corresponding to relative densities of 18–30%.     

Porous anorthite ceramics with ultra-low thermal conductivity

Porous anorthite ceramics with an ultra-low thermal conductivity of 0.018 W/m K have been fabricated by hydrous foam-gelcasting process and pressureless sintering method using γ-alumina, calcium carbonate and silica powders as raw materials. Microstructure and phase composition were analyzed by SEM and XRD respectively. Properties such as porosity, pore size distribution and thermal conductivity were measured. High porosity (69–91%) and low thermal conductivity (0.018–0.13 W/m K) were obtained after sintering samples with different catalyst additions at 1300–1450 °C. Porosity, pore size, pore structure and grain size had obvious effect on heat conduction, resulting in the low thermal conductivity. The experimental thermal conductivity data of porous anorthite ceramics were found to be fit well with the computed values derived from a universal model.     

Low sintering shrinkage porous mullite ceramics with high strength and low thermal conductivity via foam-gelcasting

Excessive sintering shrinkage leads to severe deformation and cracking, affecting the microstructure and properties of porous ceramics. Therefore, reducing sintering shrinkage and achieving near-net-size forming is one of the effective ways to prepare high-performance porous ceramics. Herein, low-shrinkage porous mullite ceramics were prepared by foam-gelcasting using kyanite as raw material and aluminum fluoride (AlF₃) as additive, through volume expansion from phase transition and gas generated from the reaction. The effects of AlF₃ content on the shrinkage, porosity, compressive strength, and thermal conductivity of mullite-based porous ceramics were investigated. The results showed that with the increase of content, the sintering shrinkage decreased, the porosity increased, and mullite whiskers were produced. Porous mullite ceramics with 30 wt% AlF₃ content exhibited a whisker structure with the lowest shrinkage of 3.5%, porosity of 85.2%, compressive strength of 3.06 ± 0.51 MPa, and thermal conductivity of 0.23 W/(m·K) at room temperature. The temperature difference between the front and back sides of the sample reached 710°C under high temperature fire resistance test. The low sintering shrinkage preparation process effectively reduces the subsequent processing cost, which is significant for the preparation of high-performance porous ceramics.     

Porous ceramics with near-zero shrinkage and low thermal conductivity from hazardous secondary aluminum dross

Herein, a simple, versatile, and low-cost approach has been proposed to realize the green utilization of secondary aluminum dross, the hazardous solid waste, namely directly sintering dry-pressed green bodies from secondary aluminum dross to fabricate porous ceramics according to high-temperature foaming process spontaneously without adding spare foaming agents. Aluminum nitride (AlN) in secondary aluminum dross was employed to realize high-temperature foaming due to its oxidation, which makes traditional AlN and salts removal process needless. Moreover, near-zero shrinkage or even expansion during sintering of porous ceramics have occurred because in-situ foaming process together with the oxidation of Al particles well offset the sintering shrinkage. After sintering at 1400°C for 2 h, porous ceramics composed of α-Al₂O₃ and spinel phases with open porosity of 37.91%, sintering expansion rate of 1.13%, flexural strength of 45.67 MPa, and thermal conductivity of 0.97 W/(m·K) have been prepared. Cenospheres as pore-forming agents have been added to further improve the porosity, and alumina-based porous ceramics with open porosity of 28.39%–43.20% and flexural strength of 15.80–52.48 MPa have been obtained. This effective solution for recycling secondary aluminum dross could supply high-performance porous ceramics, which is expected to be applied in the fields of light-weight structural components and thermal insulations.     

Ultra-low cost porous mullite ceramics with excellent dielectric properties and low thermal conductivity fabricated from kaolin for radome applications

Near-net-shape mullite ceramics with high porosity were prepared from ultra-low cost natural aluminosilicate mineral kaolin as raw material and polystyrene micro-sphere (PS) as pore-forming agent. Microstructure, flexural strength, thermal conductivity and dielectric properties of the ceramics were systematically researched. Results show that the porous mullite ceramics possess fibrous skeleton structure formed by a large quantity of interlocked mullite whiskers, which results in good mechanical properties and low-to-zero sintering shrinkage. Flexural strength of the porous mullite ceramics can be up to 41.01 ± 1.12 MPa, even if the porosity is as high as 62.44%. The dielectric constant and loss tangent of the porous mullite ceramics at room temperature are lower than 2.61 and 5.9 × 10⁻³, respectively. Besides, dielectric constant is very stable with the rising of temperature, and the dielectric loss can be consistently lower than 10⁻² when the temperature is not higher than 800 °C. In addition, thermal conductivity at room temperature is as low as 0.163 W/m/K when the porosity of mullite ceramics is 80.05%. The infiltration of SiO₂ aerogels (SiO₂ AGs) can further decrease the thermal conductivity to 0.075 W/m/K, while has just little effects on the dielectric properties. Excellent mechanical, thermal and dielectric properties show that the porous mullite ceramics have potential applications in radome fields. The porous mullite ceramics prepared from kaolin not only have low cost, but also can achieve near-net-shape.     

Acoustic emission studies of low thermal expansion aluminum-titanate ceramics strengthened by compounding mullite

Mullite (Mu) with high strength was compounded into aluminum-titanate (AT) ceramics with low thermal expansion to increase their strength. For the AT–Mu system composites, thermal contraction and expansion and acoustic emission (AE) event count rate were measured during cooling using the AE technique and the characteristics of AT–Mu composites were evaluated. The expansion due to microcracking in the range of AE count peak temperatures to room temperature was obtained and the crack volume was estimated from the expansion by cracking. A linear relation with a very high correlation (r = 0.993) was observed between bending strength and crack volume at room temperature. From the linear plot, the bending strength at crack-free temperature in the best AT–Mu composite was shown to be 130 MP.     

High thermal conductivity silicon nitride ceramics prepared by pressureless sintering with ternary sintering additives

Silicon nitride ceramics were pressureless sintered at low temperature using ternary sintering additives (TiO₂, MgO and Y₂O₃), and the effects of sintering aids on thermal conductivity and mechanical properties were studied. TiO₂–Y₂O₃–MgO sintering additives will react with the surface silica present on the silicon nitride particles to form a low melting temperature liquid phase which allows liquid phase sintering to occur and densification of the Si₃N₄. The highest flexural strength was 791(±20) MPa with 12 wt% additives sintered at 1780°C for 2 hours, comparable to the samples prepared by gas pressure sintering. Fracture toughness of all the specimens was higher than 7.2 MPa·m^1/2 as the sintering temperature was increased to 1810°C. Thermal conductivity was improved by prolonging the dwelling time and adopting the annealing process. The highest thermal conductivity of 74 W/(m∙K) was achieved with 9 wt% sintering additives sintered at 1810°C with 4 hours holding followed by postannealing.     

Rare-earth-tantalate high-entropy ceramics with sluggish grain growth and low thermal conductivity

A series of rare-earth-tantalate high-entropy ceramics ((5RE_0.2)Ta₃O₉, where RE = five elements chosen from La, Ce, Nd, Sm, Eu and Gd) were prepared by conventional sintering in air at 1500 ^°C for 10 h. The (5RE_0.2)Ta₃O₉ high-entropy ceramics exhibit an orthogonal structure and sluggish grain growth. No phase transition occurs in the test temperature of 25–1200 ^°C. The thermal conductivities of all (5RE_0.2)Ta₃O₉ ceramics are in the range of 1.14–1.98 W m^?1 K^?1 at a test temperature of 25–500 ^°C, approximately half of that of YSZ. The sample of (Gd_0.2Ce_0.2Nd_0.2Sm_0.2Eu_0.2)Ta₃O₉ exhibits a low glass-like thermal conductivity with a value of 1.14 W m^?1 K^?1 at 25 ^°C. The thermal expansion coefficient of (5RE_0.2)Ta₃O₉ ceramics ranges from 5.6 × 10^?6 to 7.8 × 10^?6 K^?1 at 25–800 ^°C, and their fracture toughness is high (3.09–6.78 MPa·m^1/2). The results above show that (5RE_0.2)Ta₃O₉ ceramics could be a promising candidate for thermal barrier coatings.     

Macroporous mullite materials prepared by novel shaping strategies based on starch thermogelation for thermal insulation

A rigorous microstructural analysis of porous mullite materials developed using novel shaping strategies based on the starch consolidation casting, and their thermal properties in relation to the processing and starch type were accomplished in view of their use as thermal insulators. In order to characterize the size and morphology of pore, basic size and 2D shape factors, and global 3D stereological parameters were determined using microscopy techniques. Results indicated that the porosity volume, pore connectivity degree, and mean free path were the determining factors of the lowest heat transfer by conduction registered in materials prepared with cassava starch. This material is the best candidate to be used in thermal insulation.     

Fibrous porous mullite ceramics modified by mullite whiskers for thermal insulation and sound absorption

In order to meet the demand for thermal insulation and sound absorption, fibrous porous mullite ceramics (FPMC) with high porosity and an interconnected pore structure were prepared, followed by a pore structure modification with in situ grown mullite whiskers on the three-dimensional framework of the FPMC. The resultant hierarchical material exhibited superior sound absorption performance in the low-to-medium frequency to most reported sound-absorbing materials, as well as a sufficient compressive strength of 1.26 MPa with low thermal conductivity of 0.117 W·m^?1·K^?1. Moreover, the effects of solid content and mullite whiskers on the microstructure and physical properties of the material were analyzed. The increase of solid content led to increased compressive strength and thermal conductivity and decreased frequency corresponding to the first sound absorption peak. The thermal conductivity and compressive strength of the material increased as the mullite whiskers grew, while the median pore size decreased.     

Porous alumina ceramics prepared with wheat flour

It is shown that wheat flour can be used as a pore-forming and body-forming agent in ceramic technology. In contrast to pure native starch, however, the pores do not result from the swelling starch granules alone but are mainly due to protein-assisted foaming. Therefore the porosity is significantly higher and the pore size larger than that resulting from the starch granules alone, and the wet milling time applied for homogenizing the ceramic suspensions becomes the most critical process parameter. Alumina suspensions with 70 wt.% alumina and 20–30 vol.% wheat flour with different initial particle size (fine grade and semolina, respectively) have been prepared using milling times of up to 8 h. Porosities of up to approx. 60% can be achieved with only 20 vol.% of flour or semolina after 8 h of milling time, with the cell sizes (diameters of pore cavities resulting from foam bubbles) being essentially independent of the milling time (median diameters of 120–240 μm). Effective pore throat sizes (i.e. diameters of cell windows or channels between cells), measured via mercury porosimetry, are 1–2 μm for short milling times (2–3 h), but for long milling times (8 h) they change by more than one order of magnitude to median sizes of 20–30 μm, closely corresponding to the median size of wheat starch granules (approx. 20 μm).     

Cellular silica-based ceramics prepared by direct foaming at high temperature

Cellular silica-based ceramics, including Si₃N₄/SiO₂ composite ceramics and monolithic silica ceramics, with dense shell and closed cells with dense and crack-free cell wall inside was prepared by the direct foaming of the green-compacts at 1310–1370 °C. The influences of the heat-treatment temperature on the relative density as well as the mechanism of the cell formation were investigated. The porosity of the obtained cellular silica and Si₃N₄/SiO₂ ceramics was within 60.0–84.0%, the cell size distribution was in the range of 10–120 μm, and the flexural strength was 9.7–16.3 MPa.     

Porous ceramics with controllable properties prepared by protein foaming-consolidation method

A new protein foaming-consolidation method for preparing porous alumina was developed using egg yolk both as consolidating and foaming agent. This method allows the control of properties of porous alumina not only by varying alumina-to-yolk ratio but also by managing the foaming process. After drying, the green bodies were burned at 600 °C for 1 h to remove the pore creating agent, followed by sintering at 1,550 °C for 2 h. The porous alumina ceramics with pore sizes of 25–1,000 μm and relative density of 29–50% were obtained. The compressive strength of the sintered samples varied within the range of 1.1–5.7 MPa, corresponding to porosity of 40–71%. The addition of dispersant with different concentration into alumina slurries shifted the rheological properties from shear thinning behavior to a Newtonian fluid, which resulted in changes in the pore sizes of the resulting ceramics. The main advantages of the process are the simplicity of the process and the low-cost processing equipment/materials needed. These results have opened a novel preparative way for porous ceramics especially alumina-based porous materials designed for biomedical applications.     

Thermal conductivity of porous alumina ceramics prepared using starch as a pore-forming agent

The thermal conductivity of porous alumina ceramics prepared using different types of starch (potato, wheat, corn, and rice starch) as pore-forming agents is investigated from room temperature up to 500 °C. The temperature dependence measured for alumina ceramics of different porosity (in the range 6–47%) is fitted with second-order polynomials and 1/T-type relations, and compared to available literature data for dense alumina. It is found that the porosity dependence of the relative thermal conductivity k_r = k/k₀ is well described by a modified exponential relation of the form k_r = exp(?1.5?/(1 ? ?)), where ? is the porosity. This finding is in agreement with other literature data and seems to indicate a common feature of all porous materials with microstructures resulting from fugitive pore-forming agents.     

Processing and properties of silica-bonded porous nano-SiC ceramics with extremely low thermal conductivity

Silica-bonded porous nano-SiC ceramics with extremely low thermal conductivity were prepared by sintering nano-SiC powder-carbon black template compacts at 600–1200 °C for 2 h in air. The microstructure of the silica-bonded porous nano-SiC ceramics consisted of SiC core/silica shell particles, a silica bonding phase, and hierarchical (meso/macro) pores. The porosity and thermal conductivity of the silica-bonded porous nano-SiC ceramics can be controlled in the ranges of 8.5–70.2 % and 0.057–2.575 Wm⁻¹ K⁻¹, respectively, by adjusting both, the sintering temperature and template content. Silica-bonded porous nano-SiC ceramics with extremely low thermal conductivity (0.057 Wm⁻¹ K⁻¹) were developed at a very low processing temperature (600 °C). The typical porosity, average pore size, compressive strength, and specific compressive strength of the porous nano-SiC ceramics were ∼70 %, 50 nm, 2.5 MPa, and 2.7 MPa·cm³/g, respectively. The silica-bonded porous nano-SiC ceramics were thermally stable up to 1000 °C in both air and argon atmospheres.     

Facile processing of oriented macro-porous ceramics with high strength and low thermal conductivity

Unidirectionally oriented architectures demonstrate a notable efficiency in enhancing the properties of macro-porous materials, yet are difficult to construct in a time- and cost-effective fashion. Here a facile approach was exploited for fabricating oriented macro-porous ceramic materials by employing natural graphite flakes as a fugitive material and preferentially aligning the flakes within ceramic matrices using accumulative rolling technique. Flaky to near-ellipsoid shaped pores with a homogeneous distribution were created in macro-porous zirconia ceramics with their porosity and microstructural characteristics adjustable by controlling the additive amounts of graphite flakes. The resulting materials exhibited a good combination of properties with high compressive strength up to over 1.5 GPa, which exceeds those of most other porous zirconia ceramics with similar porosities, along with low thermal conductivity of 0.92–1.85 Wm^?1·K^?1. This study offers a simple means for developing new oriented macro-porous materials with enhanced properties, and may promote their application by allowing for easy mass production.     

Effect of starch on pore structure and thermal conductivity of diatomite-based porous ceramics

Considering the low-cost and environmental protection, the porous ceramics with high porosity using natural diatomite powder were successfully prepared by utilizing hot injection moulding and sacrificial fugitives. The impacts of different content of starch as a pore-forming agent on the phase composition, mechanical properties, thermal conductivity, and micro-structure of porous ceramics were investigated. The results demonstrate that starch content can significantly affect the mechanical properties and thermal conductivity of diatomite-based porous ceramics. When the starch content increased from 0 wt % to 50 wt %, the porosity increased from 61.2% to 80%, while the thermal conductivity decreases from 0.239 W/(m K) to 0.098 W/(m K). The low thermal conductivity of porous ceramics may be related to the macroporous–mesoporous composite structure. With the starch content increased, a greater chance of starch granule contact, higher internal pore sizes and a wider pore size distribution in the prepared samples, which resulting in lower mechanical strength, such as the three-point bending strength from 2.83 MPa to 0.46 MPa.     

High-strength thermal insulating mullite nanofibrous porous ceramics

Mullite fibrous porous ceramics is one of the most commonly used high temperature insulation materials. However, how to improve the strength of the mullite fibrous porous ceramics dramatically under the premise of no sacrificing the low sample density has always been a difficult scientific problem. In this study, the strategy of using mullite nanofibers to replace the mullite micron-fibers was proposed to fabricate the mullite nanofibrous porous ceramics by the gel-casting method. Results show that mullite nanofibrous porous ceramics present a much higher compressive strength (0.837 MPa) than that of mullite micron-fibrous porous ceramics (0.515 MPa) even when the density of the mullite nanofibrous porous ceramics (0.202 g/cm³) is only around three quarters of that of the mullite micron-fibrous porous ceramics (0.266 g/cm³). The obtained materials that present the best combination of mechanical and thermal properties can be regarded as potential high-temperature thermal insulators in various thermal protection systems.     

High-strength thermal insulating porous mullite fiber-based ceramics

How to improve the strength of fibrous porous ceramics dramatically under the premise of no sacrificing its low density and thermal conductivity has remained a challenge in the high-temperature thermal insulation field. In this paper, a new kind of high-strength mullite fiber-based ceramics composed of interlocked porous mullite fibers was prepared by nanoemulsion electrospinning and dry pressing method. Results show that as to the porous ceramics with the same density (～ 0.8 g/cm³), the three-dimensional skeleton structure composed of porous mullite fibers was much denser than that composed of solid mullite fibers. Therefore, porous mullite fiber-based ceramics exhibited a higher compressive strength (5.53 MPa) than that of solid mullite fiber-based ceramics (3.21 MPa). In addition, porous mullite fiber-based ceramics exhibited a superior high-temperature heat insulation property because the porous structure in fibers could reduce the radiant heat conduction. This work provides new insight into the development of high-temperature thermal insulators.     

Porous YSZ ceramics with unidirectionally aligned pore channel structure: Lowering thermal conductivity by silica aerogels impregnation

The previous report of this work has demonstrated the fabrication and properties of porous yttria-stabilized zirconia (YSZ) ceramics with unidirectionally aligned pore channels. As a follow-up study, the present work aims at lowering the thermal conductivity of the porous YSZ ceramics by silica aerogels impregnation. The porous YSZ ceramics were immersed in an about-to-gel silica sol. Both the unidirectionally aligned pore channels and the inter-grain pores by grain stacking in the channel-pore wall of the porous YSZ ceramics were impregnated with the silica sol. After aging and supercritical drying, silica aerogels formed in the macroporous network of the porous YSZ ceramics with unidirectionally aligned pore channels. The influences of silica aerogel impregnation on the microstructure and properties of porous YSZ ceramics with unidirectional aligned pore channels were investigated. The porosity decreased after impregnation with silica aerogels. Both microstructure observation and pore size distribution indicated that both channel-pore size and inter-grain pore-size decreased significantly after impregnation with silica aerogels. Impregnating porous YSZ ceramics with silica aerogels remarkably lowered the room-temperature thermal conductivity and enhanced the compressive strength. The as-fabricated materials are thus suitable for applications in bulk thermal isolators.